This study focused on constructing a high-solid reaction system to prepare type 3 resistant starch (RS3) with high-amylose maize starch as raw material by mechanical activation (MA) pretreatment combined with thermal and freeze–thaw treatments. MA pretreatment effectively destroyed the crystal structure and molecular structure of native starch. MA damaged starch with a certain viscosity could form dough with a small amount of water to construct a starch continuous phase system. RS content increased with the damage levels of starch as the formation of double helix structure, attributed to that the molecules of MA damaged starch could be easy to move and form recrystallization structure. Thermal and freeze–thaw treatments contributed to strong interaction of starch–water and the re-formation of internal crystal structure of MA damaged starch to form RS3. This study provides insight into the development of a highly effective approach for large scale production of resistant starch.